AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

...........5 Application tips ..................................................13 3...................................5 Limitations for the use of the cell without diaphragm...............................................28 4....4 1...........18 3................................................................................3.............................................................................29 4..1 An historic overview .................................................14 3.........36 4.......26 4.........................4.....................................................................................4 1............38 5 Sampling .......................................3 Concentration determination with Water Standard 10.........................................................19 3..........................................1.......................1.......................33 4........................4 Generator electrode without diaphragm ...........................................................................................4 Polarization current and end point..........................1 Principle of bipotentiometric indication ..................3 Stirring speed and dispersion of the volumetric KF titrant.....................2..............1..3........................................METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration .......11 2...............................................1 The influence of atmospheric humidity (drift determination) .........4 Concentration determination with pure water.............................16 3..........................2 The minimum and maximum dosing rate .1 Volumetric KF reagents................4.........2......................1..........3 Pyridine-containing reagents ............................................................................29 4...............21 3.......6 Dissolving capacity of the solvent ....................4 Control parameters in the volumetric KF titration ....2............5 Control paramaters in the coulometric KF Analysis ........3 Consequences for practical applications..................................................4 Cleaning the coulometric KF titration cell.....................7 2....13 3................................................................1.................................4..........................6 2 Volumetric and Coulometric Karl Fischer Analyses ...............................................2 Two-component KF reagent .......33 4..............................................3 The Cautious start ...............................2 The Karl Fischer chemical reaction ....39 1 ...................................................19 3........................................................................................1 Filling the coulometric cell ......2 End point and polarization current................................................8 2............................................................................................................................................................5 1....13 3....................................................................................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration ...........18 3.................................................2............................2.......8 2.............................3........24 4.........................................................................33 4......................................................................................4...............11 2.............2 Stoichiometry of the coulometric KF rection ......2 When do you have to replace the electrolyte? ...3......................................................................7 2....................27 4................................................9 2.....................................2 Coulometric KF analysis....2.32 4..............3 Volumetric KF Titration: Titrant concentration..................................................9 2........................2 Reaction rate .......................26 4....26 4.......................................... The Karl Fischer titration............6 Termination parameters for both coulometric and volumetric KF titration....1.................................0 mg/g ........................10 2.......22 3...........................................4.....20 3....12 3 Titration control and end point determination.....................16 3............3................................................................................2 Working with the coulometric KF instruments ...................1 The Control Band ...5 Cleaning the measuring electrode .........35 4.............6 General recommendations .........................3.........9 2............1 KF coulometry ...............5 The solvent..............21 3..........3 Iodine generation.......6..........................................................7 2..................1 Titration stand ......2.............................1 Indication ...............................................1 One-component KF reagent .................4..................................................................................................2 The drift .....8 2........................1..............................................5 Karl Fischer reagents with ethanol .......1.34 4...........2...4 Special reagents for aldehydes and ketones.................2...........2 Concentration determination with di-sodium tartrate dihydrate......3 Secure draining and filling of the titration cell: SOLVENT MANAGER........................................................................................1....................................2..........................28 4..............................................................19 3................37 4.....................1 How often should the concentration be determined?..................

.................................................................................................................inorganic ...............1.................................................2.....................................................................................................................................2 Liquid samples ..............86 11...........................75 11 Karl Fischer Titration: The Method at a Glance ..................................2 Measurement accuracy.......................................................................5 Additional literature ..........................3 Amount of sample ................2 Reaction with water.......3...................2 Inorganic chemicals ..........................................85 11.....................................3 Technical products – organic ...............................................................................55 7..............77 11........................................................................................3 Reaction with iodine ...........3 Procedure..........................4 Sample preparation and input ........................77 11................71 9......................................39 5..................................1 Liquid samples ...................................................................................................1...............................................................................................3 External dissolution ..........6.....................................................87 11................................................83 11....................................................6 Food ...............45 7 Release of water from the sample ........................................................................4...............................................68 9 Interferences ..............3 Repeatability .....................................1 Coulometry..............................................................................................................54 7............2 Solids: Sample input ................1 Reaction with methanol.................................................................................43 6.....................................................................................................................................................6..............................................................5 Determination of water in gases ........................................4 Lyophilized substance in septum bottles................80 11......5 Technical natural products ..............................................58 7.........4 Manual Karl Fischer drying oven..................................58 7........................................83 11...............1 Principle .........................................6............................................................................70 9....................73 10............................87 11.............................................................2 Solid samples.......79 11......4 Example: reevaluation of side reactions .................5 STROMBOLI automatic oven sample changer ......1 Internal extraction ..............77 11...........................................58 7.......................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5....................................................................................90 2 ............................71 9..............................................................4....................................71 9.............................................................................1................................................................................1 Taking the sample............................................................................49 7..................................2 Foods and technical products ...............................2..2 External extraction ..............................79 11.............................5 Accessories for sample input ...........................................3 Liquids: Characteristics ..........................................................2.....3...............................................................................................................3 Titration Methods ..............................2 Coulometric methods .............................47 7...............................................................................................2 Side reactions .....................4 Liquids: Sample input..............................................................................................................................................1 Organic Chemicals..............................................................................................1 Solid samples.........62 8 Measurement results ...................................................................59 7..................67 8..1.............................60 7.........................57 7.............87 11...................40 6 Sample addition .....................................................................1 Volumetric methods ...........................1..................39 5..........81 11............................78 11........................1 Effects of temperature....................1...86 11........................................................................................43 6.........................................4....................86 11............................................6 Determination using the drying oven ..........................................................................73 10...............70 9..............48 7..............67 8.........................4...............................................89 12 Appendix ........................................................................................................................................................................................................................2 Purge gas..........6 References......................70 9.........2 Storing the sample .............................................................4............6....................................................79 11......................................2.....................2 Volumetric Karl Fischer Titration ................78 11...............................................................4 Technical products .............................................................................................................................................................................1 Resolution and detection limit .....80 11.....1 Solids: Characteristics................4...........6......67 8........................................................................1 Organic and inorganic chemicals ..............72 10 Troubleshooting .................................................................................88 11..........................

......................................................93 12.......3 Standards for Karl Fischer coulometry...............................90 12................................6........................................................................................2 Two-component reagent: ....91 12.3 For samples that are insoluble in methanol or ethanol ........98 13.............6.......................4 Safety data for the KF-components and auxiliary solvents: ...................................................................4 For ketones and aldehydes...............97 13 Hazards and waste disposal tips ........96 12........................3 Reagents for coulometry: .........................95 12........6 Titrants and solvents for volumetric analysis ..................................95 12....98 13....4 For ketones and aldehydes............91 12...............................92 12..............................................2 For samples that are poorely soluble in methanol or ethanol ...........92 12..................................3 For samples insoluble in methanol or ethanol.....96 12.........................95 12..............................98 13.....................98 3 ........................4 Reagents and solvents for coulometric analysis .......5 For acids and bases (pH value) ................1 For samples soluble in methanol or ethanol .....................95 12............................4..........92 12.............................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12....................4......................................................1 Formula for the external extraction ....................................................5 Water Standards for Karl Fischer volumetric titration...............6........................................................................................94 12.............................93 12................................................1 One-component reagent .............5 For acids and bases (pH value) ..............................................4.............2 For samples poorly soluble in methanol or ethanol...........4..........................2 Formula for the external dissolution ............................4..........98 13......................................6........................................................1 For samples that are soluble in methanol or ethanol ........................................6.........................

DL37 KF Coulometer from METTLER TOLEDO. Automatic KF titration instruments with piston motorized burettes. Publication: “The Dead-Stop End Point“. M. Introduction of less poisonous KF reagents based on ethanolic solution.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1].Boyd [4]. First diaphragm-less cell for coulometric KF titration. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. titrant specific standard parameters and LEARN titration. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. respectively. S. Solid KF Oven Standards with water contents of 5. Hopkinson [2]. Water standards (10. Pyridine-free KF reagents are commercially available.1 mg/g) with test certificate according to DIN 50049-2. by G. April 1956. First coulometric KF titration instruments are commercially available. 2000 2001 2002 2008 4 . They replaced the DL18/35 KF Volumetric Titrators. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. Publication: Coulometric Karl Fischer Titration by A.5% and 1%. 1.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. and solvent dispensing and removal.0. L. Meyer and C. First German DIN standard for the Karl Fischer titration (DIN 51777. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer .0. Peters and J. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. D.J. promoted by publications by E. Use of Karl Fischer method spreads. Wernimont and F. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination.Direct method”).METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. 0. Jungnickel. Publication on stabilized single-component Karl Fischer reagent by E. Eberius [3]. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. Enormous spread of the use of KF titration.

Methanol proved to be suitable as a solvent. but rather the methyl sulfite ion. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. and the faster the rate of the Karl Fischer reaction. I2 + SO2 + 3 Py + H2O → 2. In an alcoholic solution.. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1.5. the maximum reaction rate is reached here and cannot increase further. Bryanz and Mitchell [6] formulated a two-step reaction: 1. the more methyl sulfite is formed by the capture of protons. all the sulfur dioxide is present as methyl sulfite. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations.5 to 8.e. The rate of the Karl Fischer reaction. In the pH range 5. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). In order to achieve an equilibrium shift to the right. I2 + SO2 + 3 Py + H2O → 2. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. W. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. Karl Fischer used pyridine for this purpose. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. At pH values above 8. i. Verhoff and E. described by the rate constant k. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. Smith. In an alcohol-free solution. methanol not only acts as a solvent but also participates directly in the reaction itself. the 5 . C. it only acts as a buffering agent and can therefore be replaced by other bases.

g. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. diethylene glycol monoethylether) [10. 6 . Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. ethanol.C. this results in a more sluggish endpoint and higher iodine consumption. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. J. Verhoff and E. This improves the titer stability. methoxyethanol. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. On the basis of this knowledge. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. With acidic or basic samples.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5. This. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. ROH + SO2 + RN 2. and for bases: salicylic acid). A. Methanol should therefore always be present in the minimum required amount. you can use other alkohols such as. for instance. This reagent not only replaced the toxic. methanol) (e. In 1988.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions.g. for determination in ketones or aldehydes). Studies by E. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. pungent pyridine. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. and references therein]. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. If a methanol-free titrant has to be used (e. pH values less than 4 and greater than 8 should be avoided in practice. 2-propanol.g. is not a serious limitation because the water concentration in the solvent is usually much less. in a titration. however. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. E.g. ethylene glycol monomethyl ether. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e.5 to 8.

METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. The reagent can be stored for approximately two years. i. Coulometric Karl Fischer Analysis. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. The solvent is methanol. where a solution containing iodine is added using a motorized piston burette. Suitable for samples where water is present in trace amounts: 1 ppm . You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. The drop in titer. 7 . dissolved in a suitable alcohol. the decrease in concentration. Suitable for samples where water is present as a major component: 100 ppm . 2 mg/mL for samples with a water content of less than 1000 ppm. sulfur dioxide and imidazole..5% 2.1 One-component KF reagent The titrant contains iodine.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration.5 mg/mL per year in a sealed bottle. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. is approximately 0.1.e. 1 mg/mL for samples with a water content of less than 200 ppm.1 Volumetric KF reagents 2.

Note that it may be necessary to adapt the end point value in the titration method to these reagents. from VWR/MERCK) are commercially available to prevent this problem. imidazole and methanol. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. This special reagent is also suitable for substances that react with methanol. provided that the bottle is tightly sealed. The solvent is either methanol or consists of methanol mixtures.g.1. sulfur dioxide and pyridine. stable titer. e.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. The titration takes slightly longer than with the standard KF reagent. or an alcoholic mixture. One-component reagent: The titrant contains iodine. methanol). dissolved in an alcohol (usually methanol).2 Two-component KF reagent The titrant contains iodine and methanol.1. pyridine. increases their lifetime. Solvent capacity restricted. Both the components are very stable in storage. sulfur dioxide and 2-methoxyethanol. additional water is produced and titrated at the same time. whereas the solvent contains 2-chloroethanol and trichloromethane. The titrant has a stable titer. + Simple handling. This reagent is declared as “rapid”.g.1. favorably priced. methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. imidazole. Reagents One-component Two-component 2. methanol) and B (iodine. leading to higher water contents and a vanishing end point. 2. 8 . which allow for fast and accurate Karl Fischer titrations. The solvent contains sulfur dioxide.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. 2 mg/mL for samples with a water content of less than 1000 ppm. A titration speed two or three times as high can be achieved with the two-component reagent. reagents containing pyridine are still used because they are cheaper and can be made in-house. titration speed slower. To improve stability. The separation into titrant and solvent improves stability of the KF reagents. As a result. such as amines. e. whereas the solvent consists of sulfur dioxide and a base. High titration speed. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. These solutions are mixed 1:1 just before use to form the one-component titrant. Special methanol-free KF one-component reagents such as e.g.g. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. One-component reagent: The titrant contains iodine. dissolved in methanol. from Sigma-Aldrich) and e. Two-component reagent: The titrant contains iodine dissolved in an alcohol. – Titer less stable. HYDRANAL® (Composite 5K and Working Medium K. imidazole. and results in higher titration speed.

The generator is close to the measuring electrode*.2. however.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. whereas the solvent contains sulfur dioxide. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry.2 Coulometric KF analysis 2. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I .→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. ethanol-based reagents were launched in 1998. 9 . which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. diethanolamine and ethanol. 2. two-component.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. a double pin platinum electrode. the anode compartment and the cathode compartment. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol.1. Both parts are separated by a diaphragm. or “inner burette”) incorporated into the glass titration cell. imidazole. The classical coulometric cell consists of two parts. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. The titrant contains iodine and ethanol.

octanol. C. other solvents such e. The negative iodide ions release electrons at the anode and form iodine.e.g. releasing two electrons at the anode.→ I2 → H2O 10 . The value 96845 C/mol is known as the Faraday constant. i. it is known that to produce one mole of a chemical substance that requires one electron. Depending on the application. CH3SO3H. as chloroform. Note that methyl sulfonic acid. 96485 C of current are needed. The catholyte is either a manufacturer-specific special reagent.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. Methanol or ethanol is used as solvent. C. imidazole and iodide salts. it is necessary to first recall the definition of 1 Coulomb: one coulomb. Subsequently.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. which subsequently reacts with water. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. Cathode reaction At the cathode. iodine reacts with water.2. i. The cathode compartment contains the catholyte. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. 2 I.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb.e. or the same reagent as used in the anode compartment. 2. I2. In Karl Fischer reaction two iodide ions. is the quantity of charge that is transported by a current of 1 ampere in one second. 2 [RN]H+ + 2e. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). present in the anolyte compartment. iodine is generated from iodide by electrochemical oxidation. This consists of sulfur dioxide. are oxidized to one molecule of iodine. the positive hydrogen ions are reduced to hydrogen. I-. This is the main product formed. used to generate iodine. To calculate it. Anode reaction At the anode. This can cause the cathode to become black. hexanol or ethylene glycol may be added. An ammonium salt is added to the catholyte in order to promote hydrogen production. the catholyte should be replaced once in two weeks. 1C=1A·1s On the other hand. To avoid this.

the coulometer operates with current pulses of 400 mA.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. In addition. 2.e. the maximum possible current applied by the instrument is 100 mA. no standardization of the coulometric KF reagents is necessary. Nevertheless. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 .3 Iodine generation Iodine is generated by means of current pulses of 400. As a consequence. 2.015 g/mol.). At very low conductivities (i. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. Since the molar mass of water is 18.712 C electrical current. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. less than 3–4 μS/cm). For an electrochemically optimized Karl Fischer cell.2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. Since current and time can be accurately measured. 2 x 96485 C/mol is required for 1 mole of water. the current conversion efficiency for iodine production is assumed to be 100%.2. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. With standard conductivity values. hexanol. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10. For this reason. coulometry is designated as absolute method. 300. etc. 200 and 100 mA. it is used as a reference method for the determination of water content.

especially when easily reducible. However. To avoid this concurring reaction. 2. etc. 12 . a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. other easily reducible substances such as unsaturated fatty acids. it is still possible for a very small amount of iodine to reach the cathode.ethers ketones (with special reagent) .g.. Nascent hydrogen is formed at the cathode. In practice. a different geometry is used for the generating cell without diaphragm. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this.e. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. lower than 50 μg water/sample). The latter can thus react more efficiently with water. This effect is further enhanced by the small dimensions of the cathode.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. especially for nitro compounds such as nitrobenzene. This is a very good reducing agent. the cathode is a small-size pin). Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. the cell with diaphragm may yield more precise results. may also be reduced at the cathode by the formation of water. and for very accurate determinations. In addition.2.acetamides etheric oils and essences .edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons.phenols (most) esters . the relative error due to this effect can be minimized by using a larger amount of sample. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. Thus. for measurement of samples having a very low water content (e. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . Nevertheless.chlorinated hydrocarbons alcohols .METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally.

the control algorithm and its parameters. there will be free iodine in the titration solution. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. and the addition or production stopped exactly at the end point. . . A high voltage is necessary to maintain the specified polarization current at the electrode. • • • As soon as all the water has reacted with iodine. When the voltage drops below a defined value. The resulting titration speed depends on the following factors: .1. iodine should be added or generated as quickly as possible. there is no free iodine in the titration/anolyte solution. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry").the termination of the analysis. • • As long as the added iodine reacts with the water. A small. 3.the stirring speed and mixing of the sample solution. the water content. The control of the titration is only possible if the end point is indicated. 13 .the addition speed or generation rate of iodine .the reaction rate of the Karl Fischer reaction .1 Indication 3. and hence. .the viscosity of the solution and its temperature. Ideally. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. the titration is terminated.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled.

respectively. again.1. This free iodine gives rise to "ionic conduction". 3. 14 . Iodide ions. Above all. This drop in voltage is used to indicate the end of the titration. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. Ipol . The two negatively charged iodide ions are attracted by the positively charged platinum pin. At the end of the titration: As soon as all the water in the sample has reacted with the iodine.(to a lesser extent) the type of electrode (i. where they donate the electrons and form an iodine molecule. free iodine is present in the titration/anolyte solution. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. .METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. If mixing is poor. this value depends on the polarization current. A voltage of ca. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. i. The iodine is present only at low concentration.the polarization current. I2. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-).the solvent or anolyte used in the instrument. The end point value mainly depends on . no iodine reaches the negatively charged platinum pin. geometry and dimensions of the metal parts) . then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. which are present in excess in the titration solution. It then acquires two electrons and turns into iodide ions (2 I–). • • At the beginning and during the titration: As long as the iodine generated reacts with the water.e.e. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. there is no free iodine in the titration/anolyte solution.

Sensors with a large platinum surface. As a consequence. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. pin length: 3 to 4 mm. just after the equivalence point. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. i. The layer is formed during the first ten titrations.e. Sensors with short platinum pins (< 3 mm). With use. exhibit a larger potential jump and also a higher end point. its surface can easily bond suitable chemical compounds. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal.g. i. and increases the sensor resistance. iodine excess should be as low as possible to get accurate results. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). a double ring or plates instead of rings. This makes it more difficult to stop the titration at the right moment.4 mm. 15 . and increases the risk of over titration. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. a layer is formed on the surface of the platinum pin sensor. exhibit a smaller potential jump. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. pin length: 3 . On the other hand. with longer pins. The current density can be compared to a water pipe where a specific water has to flow. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). The larger the diameter of the pipe. However.e. In general the larger the platinum surface the smaller the current density. e. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. With used sensors. the polarization current should be set as low as possible. on the other hand. and subsequently it remains constant.

[SO2] .0 mL 1. In the volumetric KF titration. with the twocomponent reagents. It is consumed with each additional measured sample leading to a decreasing dioxide concentration. lower reaction rates are achieved with anolyte solutions that have been used for a long time.and on the iodine concentration. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. [H2O] . 2.the sulfur dioxide concentration. and overtitration may occur. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. stirring speed. Towards the end of the titration. 3. the water content is high. On the other hand.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. At the beginning. [I2] . irregular. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. the titration may also be too slow. which gives a high reaction rate.0 mL In the coulometric KF analysis.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . 3. As a consequence. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. Mixing is influenced by the 1. If 16 . shape of the vessel (volumetric KF titration).the water concentration. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant. Iodine generation or addition is usually the rate determining factor. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. point of titrant addition (volumetric KF titration).3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. If the speed is too slow. sulfur dioxide is present in large excess in the anolyte. a large excess of sulfur dioxide is present in the solvent.2 min with a titrant consumption of 2. the water concentration is lower.5 .

If a longer stirring bar is used. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. turbulence is not achieved and the mixing effectiveness is lower.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. the stirring speed is too fast. leading to slower addition and longer titration time. Bubbles falsify the measured values. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. This is essential for a fast reaction rate and for short titration times. 17 . Otherwise the sensor may directly detect added iodine. Iodine would not be distributed upwards. Furthermore. but rather along the base directly towards the sensor.

4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal.1 The Control Band The control band is a modifiable control parameter for both types of KF reagents. The following drawing reveals a schematical illustration of the control band: 18 . The dynamic behaviour of the control can be influenced by a variation of the control band. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3.4.

With large amounts of water. The maximum dosing rate is dependent on the actual burette size. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control. sensors with very short platinum pins (< 3 mm).The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. The following points represent possible contributing factors: contaminated or old sensors. Thus.. the titrator automatically issues a warning. The closer the potential to the end point. 3. In the cautious mode. the titration will take too long. Recommendations 1. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. 3. 19 . e.g.4.4 Polarization current and end point Each end point is valid for a specific polarization current. 3. In this case you can activate the Start: Cautious parameter. Dosing rate (max) = 2 mL/min. however. the titration starts so quickly that overtitration may occur.3 The Cautious start If the water content is very low. at higher water contents. which leads to a stronger reduction of the dosing speed.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. the titration starts with a slower acceleration (ramp up) than in the normal mode. This is more suited for small water amounts. 2.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. if the control band width is decreased. the control reacts more sensitively to potential changes. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. the slower is the titrant addition. i. if the polarization current changes.4. the end point must be adjusted. The end point for a specific polarization current is influenced by the sensor and the solvent. In particular.4.

This measure allows the system to cope with the reduced conductivity. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. This results in a lower voltage required to maintain the polarization current. the system reacts slowly in the case of ethanol based reagents.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. which will lead to long titration times and to low precision. this results in an illdefined titration end point.g.g. used as solvent. Auxiliary reagents • If formamide is added to the solvent. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. 2-propanol. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. 20 . • If 1-comp titrants are used. If 2-comp ethanolic reagents are used. Ethanol-based reagents • Compared to the methanol-based reagents. • If Chloroform or Xylene is added in order to dissolve oil samples. • If 2-comp titrants are used.4. If one-component reagents are used.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. the titration curve is more or less flat towards the end. e. up to 8 mL/min for most 2-Comp 2 titrants. • • If 1-Comp titrants are used with Ethanol (e. Composolver E) the standard 1-Comp parameters (cf. the titration can be accelarated by reduction of the control band to 300 mV. Therefore it is recommended to decrease the polarization current to about 15 μA. 3. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. table) work fine. instead of methanol or ethanol. setting up of the titrant as 1-comp KF titrant yields shorter titration times. In order to achieve a good repeatability. the overall ionic conductivity is decreased. the overall ionic conductivity is increased. the sensor current shall be reduced to 15 μA.

g. 2. In most cases 300 – 400 mV are well-suited. an increase of the control band is recommended. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. However the control band shall not exceed the start potential. If the titration takes too long. which is the case in 1-Comp systems. 2-methoxyethanol. Cautious Generator current: Automatic. 300. 200. In general. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. which is the case in some ethanolic reagents. The minimum dosing rate shall be used to fine tune the final phase of the titration.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. 3. E E t Oscillating system behaviour.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. Fix (400. 3.4. There is no need to accurately adjust the control band to the actual start potential. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. where the methanol has been replaced by e. the 1-Comp control is suitable for systems that show an oscillating potential behaviour.6 General recommendations 1. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. 100 mA) 21 .

the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. 3. Five termination parameters can be defined in the titration method: delay time. as soon as the was potential value was lower than the set end point during the defined delay time.. minimum titration time 22 . less than 50-100 μg water per sample). Cautious: Suitable for samples of low water content (e. iodine is generated by means of current pulses of 400. 300. More specifically. The closer the measured potential value from the predefined end point is. i.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point.25 µL for a 5 mL burette). 2. relative drift stop. and improved KF titration stands (i. This parameter shortens the titration time and leads to repeatable results.Fix). Initially. then the titration was stopped. Later on. 200 and 100 mA. Normal: This iodine generation mode is generally used for all water content determinations.e. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. The iodine generation starts slowly.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. Variation of pulse length (time). pulse frequency and pulse height (mA) are used as variables by the instruments. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. the slower is the generation of iodine. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter.e. a delayed switch-off time of 10 to 20 seconds was set at the end point.e. high resolution burettes (0. the slope of the iodine generation rate is flat at the beginning of the titration. In particular. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. In addition. tightly sealed stand). i. Since the first developed KF reagents reacted slowly. pyridine-free reagents with a faster reaction rate.e. i. maximum titration time. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. the iodine generation is higher than in the cautious mode. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. absolute drift stop. or it can be set to a specific value (“Generator current” .g.

15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. titrant concentration (volumetric) and side reactions. otherwise the termination criterion is never satisfied. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. Disadvantage: The value optimized to the initial drift. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. Thus. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. especially if working with the KF sample oven.e. easy to understand (volumetric). has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. Typical value for the relative drift stop = 2-5 μg/min (coulometric).g. Typical absolute drift stop value: 3 µg/min (coulometric). . Typical delay time: 5 . the titration is terminated and the result is printed. • Advantage: This parameter ensures a high repeatability of the results. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. After the defined time has elapsed.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e.Maximum titration time The titration is terminated after the defined time. the absolute drift stop value must be greater than the initial drift. 23 . otherwise the termination criterion will never be reached. 15 s) following the addition or generation of iodine.m the drift before titration) and the relative drift. The smallest increment must be sufficiently large to compensate the drift.

This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). and the titrant concentration (volumetric). The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular.. Use the drift/time curve to determine this value. volumetric). possibly resulting in poorer repeatability and lower water contents. soluble samples You should normally choose the relative drift stop as a termination parameter.6. Thus. The final traces are only extracted very slowly. It is recommended to be used for substances that release water slowly. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. • Advantage: This parameter ensures a high repeatability of the results. 3. The vaporization of water is also irregular in the final stages. you can ignore these traces. Maximum titration time for determinations with the KF drying oven When using the drying oven. If the water content is relatively high.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. i.METTLER TOLEDO Good Titration PracticeTM in KF Titration . A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. A relative drift stop of 20 to 30 µg/min shortens the titration time. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. so 24 . the drift at the end is often greater than the initial drift. this is the simplest and most universal parameter to use. but involves a risk that the titration will be terminated a bit too early. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability.e. This parameter is independent of the the initial drift (coulometric.

A combination of the relative drift stop and the maximum titration time has proved effective for such samples. If the drift is greater than 10 µg/min. If the drift stop value is not reached. the maximum titration time has proven to be best termination criterion in practice. The higher drift is therefore influenced to a large extent by the sample. (Set the minimum titration time equal maximum titration time). Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. 25 .METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. Therefore. you should take measures to reduce the drift. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. the titration is terminated at the latest after the defined maximum time. It gives you the best accuracy and repeatability of results.

The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . After the anolyte (coulometer) or the solvent (volumeter) has been added. 26 . The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. however. until it is absolutely free of water. the titrant and the titration stand. i. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent).1. Briefly. When you assemble the titration stand for the first time. However. the higher the atmospheric humidity in the laboratory.4 weeks (indicated by a colour change of the indicator of the silica gel). This problem is particularly relevant in tropical climates or in coastal regions. The air-conditioning system should therefore be equipped with a moisture condenser. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. the relative humidity increases. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. since cold air cannot absorb as much moisture. The air within the titration vessel also contains moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). where the relative humidity can achieve values of more than 80%.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. Moisture can enter the sample. it is titrated to dryness during pretitration. Silica gel can be regenerated over night at 150 °C. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. The following rules should be observed: • • Close all openings in the titration stand. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. the residual moisture dissolves more rapidly into the anolyte (solvent).e. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. The drift.3 hours. Condition the titration cell before use. there will be moisture on the glass surface of the titration cell and the inserts. whereas molecular sieves require temperatures up to 300 °C. This can take 1 . In this way. the greater is its influence on the results of the Karl Fischer titration.

Therefore. This is achieved by titration of the dry solvent for a defined time (drift determination). Therefore it must be taken into account when calculating the water content. On the other hand. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. the drift indicates the quantity of water that enters the titration stand over a defined period.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. it is also possible to use the value of a previously performed drift determination (“Determination”). On the other hand. it is necessary to quantify the amount of water entering the titration cell during titration. and is given in μg water/minute. In this respect. the last measured drift value is automatically stored.2 The drift No titration stand is completely water tight. the KF titrator continuously titrates the water that diffuses into the cell. and its value is displayed on the screen. For accurate results. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . or a fixed value can be defined into the titration method (“Fix value”).(drift * titration time).1. At the start of a sample titration. In the standby titration. traces of water will always find a way into the titration cell. this water amount is also titrated during analysis. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . t.

However.2. The catholyte always contains traces of water.The generator electrode should dip approx.Then fill the anode compartment with approx. . the level of the anolyte drops due to evaporation. 2. By ensuring that the level of the anolyte is higher than the one of the catholyte. This can be avoided as it follows: 1.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. If the level of the catholyte is the same or higher.Take approx. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. .Make sure that the level of the anolyte is approx. the level of the anolyte increases. If this is not the case.5 mm higher than that of the catholyte. Higher anolyte level → low drift Lower anolyte level → drift is high . 28 . In this case.5 cm into the electrolyte solution.Pour approx. . 100 mL anolyte. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. 3 . • Titration cell with diaphragmless generator electrode . you must add some methanol or sample so that the color changes to yellow.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. which leads to a higher drift. some anolyte solutions contain an excess of iodide and the solution has a brown colour.1 Filling the coulometric cell • Cell with generator electrode with diaphragm . a flow occurs from the cathode compartment to the anode compartment. the anolyte should be topped up from time to time with anhydrous methanol.2 Working with the coulometric KF instruments 4. the levels slowly become the same. . As soon as the stirrer is switched off. 100 mL electrolyte solution (anolyte) into the titration cell. Note: In production.When a sample is injected into the anode compartment. 2.First transfer 5 mL catholyte to the cathode compartment. . the moisture enters the diaphragm and is slowly released into the anode compartment. when the drying oven is used. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed.

In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. If an emulsion forms in the anode compartment. If an electrolyte is used for a long period without replacement.Anolyte solutions (100 mL): after 1000 mg water.g. If the drift is too high. . It is fully controlled by the titrator. This can lead to wrong results. below 10 μS. .2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. The capacity is monitored by the coulometers (see operating instructions).2. the worse the stirring efficiency will be. when using a generator electrode with diaphragm. A level sensor in the waste bottle prevents from overflow. With poorly soluble samples.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. • • • • • 4. After being used for two weeks. and the risk of over titration increases. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 .2. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. If the conductivity of the anolyte drops to a very low value.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. the level of the solvent or the anolyte exceeds the 150 mL mark.Catholyte solutions (5 mL): after 200 mg water. Any contact with the reagent is avoided during draining and refilling of the titration cell. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. In practice. The higher the level in the anode compartment. e. the drift slowly increases. This can happen if large amounts of samples of low conductivity are titrated.

Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen. Step 2: The Anolyte is drained into the waste bottle by applying vacuum.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. 30 .

METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . drying tube and tube holder enables both draining and refilling. An optional reagent exchange set consisting of tubes. In this configuration only draining of the titration cell is possible.

Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. Afterwards thoroughly rinse the generator electrode with water. Drying is not necessary if you use it immediately.This procedure should be repeated at least once. since it would cause a higher drift value. Simple cleaning and drying of the generator electrode Method A: .Methanol flows through the diaphragm into the cathode compartment. especially if dirty samples are analyzed. Method B: . The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. . which leads to a higher drift. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. the most effective cleaning agent is chromic acid. Moisture and contaminants are rinsed out of the diaphragm. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. then with anhydrous methanol and dry it as described above. .Fill the generator electrode with anhydrous methanol. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. If immediate use is required rinsing with anhydrous methanol shall be applied. The procedure is identical to that described above. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned. • 32 .Place the empty generator electrode in anhydrous methanol.2. The C30 provides a reagent monitoring routine which is called Reagent Control. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through. Methanol flows through the diaphragm and rinses out moisture and contaminants. .

5 Cleaning the measuring electrode Generally.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. it is better to determine the concentration every 2 to 4 hours. • Clean the platinum pin with a paper tissue.5 mol/L sulfuric acid. 4. The Ohmic resistance of the electrode is increased. This is sufficient in most cases. 2. samples may be deposited on the surface of the electrode. However. This test of the complete system by a titer determination is therefore an essential condition for accurate.g.01 mg/mL per week. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. e. the tightness of the titrant bottle and the desired level of accuracy. Their volume increases considerably with temperature. . The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. This leads to a higher potential jump. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined.2. In the global settings within the setup menu of 33 . The titrant is not chemically stable. the indicating electrode does not need cleaning. We recommend to determine the titrant concentration daily. Based on the chemical stability of the titrant. In this case. • With heavily contaminated electrodes. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0.if the titrant bottle is not tightly sealed. This also becomes noticeable through a dark coloration of the anolyte at the end point. which prevents a good indication. 3. a layer is formed on the platinum surface after the first few titrations. place the electrode in 0. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. The layer should therefore not be removed by cleaning. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) .METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. while the two-component titrant is rather stable). 4. the measuring electrode must be cleaned. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. As already described. 2) Connect the S7 connection of the generator cell with the indication electrode. so that there is a sharp drop in concentration. the one-component titrant.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant.3. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol.if the desiccant on the titrant bottle is "used up". repeatable results.

and at the same temperature.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. Under normal conditions. Since it slowly dissolves in methanol. i. Add it into the titration vessel.using the same titration stand with the same volume of solvent.04 and 0. Either the user is simply warned or the usage of the expired titrant is blocked. Note: 1. - 34 . . which prevents the execution of further titrations. Rinse the burette 2 times into a waste bottle before you determine the concentration.: . is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic. Determine the weight by back weighing and enter it as sample size.e. 4. it contains 15.Use the optimized METTLER TOLEDO method M301 Weigh between 0.3. Mix for 3 minutes to achieve complete dissolution before you start the titration. i.3 to 2. 26-50 % of burette volume. 2. Make sure that nothing adheres to the beaker wall or to the electrode.66% of water.08 g/mol).2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . Determine the concentration under the same conditions as for sample analysis. This sample size yields an optimum titrant consumption of 1. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time.e.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded.5 mL with a 5 mL burette. The plastic tubing is not absolutely water vapor-tight. Na2C4H4O6•2H2O (M = 230.

Partially soluble.3. The values that are obtained are approx. You must either change the solvent after every sample or use pure Solvent* for the determination. A cloudy solution will falsify the results (i. You can only perform one determination in 50 mL of 1:1 mixture (with 0. The values obtained are approximately 10% too high.05 g di-sodium tartrate). They are thus protected against the ingress of moisture and can be stored for up to five years. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. 35 .0 to 1.0. Less soluble. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. mixing time 2 to 3 minutes. mixing time 5 minutes. too high titer). 30% too high. Thus. mixing time 1 minute.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. mixing time 1 minute.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results.e. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. mixing time 1 minute.05 g di-sodium tartrate dihydrate). You cannot perform more than one determinations in 40 mL of ethanol (with 0. This content is confirmed by the test certificate enclosed with every package. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble. You cannot perform more than three determinations in 40 mL of methanol (with 0.045 g di-sodium tartrate). you should weigh in 1. You can perform six determinations in 30 mL of Solvent* before you need to change it.5 g of water standard 10. e. Partially soluble. You must perform the determination in pure methanol! Highly soluble. mixing time 2 to 3 minutes. Highly soluble.g. You must perform the determination in pure methanol! Less soluble.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water. "HYDRANAL®-Water Standard 10. The water standards are supplied in glass ampoules.3 Concentration determination with Water Standard 10. Slightly soluble.

Start the titration without any mixing time. Determine the weight by back weighing. Glass syringes are better. Inject exactly 10. 4.g. Enter 0.g.0 µL deionized water with a 10 µL syringe. the whole content of the ampoule is completely drawn into the syringe. – – – 36 .01 g as the sample size. You can use a water standard with 1.4 Concentration determination with pure water General When using pure water to determine the concentration.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. 6.01 mg (e.3. 3. 4. 5. 2. The error is minimized by rinsing and conditioning the syringe beforehand. In an open ampoule the liquid standard is exposed to air moisture. Plastic syringes may introduce a small amount of moisture.5 mL at a time as an aliquot.0 mg/g water standard. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. with a Hamilton microliter syringe). Open the ampoule shortly before the measurement in accordance with the enclosed instructions.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. a very good deal of practice and precise working is required to obtain repeatable. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. accurate results. Draw the whole content of the ampoule into the 10 mL syringe. the water content is increased and thus this will falsify the results. Thus. Use a new ampoule for each new concentration determination.1 mg does not satisfy the requirements for a repeatable titration. The content of an ampoule is sufficient for 3 to 5 determinations. Rinse a 10 mL syringe with approximately 1 mL of water standard. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. A balance with a resolution of 0. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. The sample should be weighed either using a balance with a resolution of 0. Start the titration without any mixing time. Inject 1 to 1. To reduce the influence of the atmospheric moisture. or with a 10.

ethereal oils Petrochemical products: gasoline. After setting the volume. caramel. diesel oil. beverages Cosmetics: soaps. fat Oils: edible oil. jelly bears Starch products: flour. You can use mixture of solvents to achieve complete dissolution. kerosene Pharmaceutical products: ointments. suppositories Sugar products: jelly. alcohols.5 The solvent To determine the water content in a sample. All the screws in the syringe must be tightened securely.0 µL. emulsions Petrochemical products: crude oil. transformer oil. salicylic acid Foods: honey. hydraulic oil. Only freely available water undergoes reaction with the Karl Fischer reagent. You can get rid of any bubbles in the syringe by expelling the water rapidly. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . However. ester Organic products: urea. dioxane. Always add each sample in exactly the same way. if it is absorbent. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. 2. corn. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. - 4. Solvent Methanol Max. Adjust the plunger to exactly 10. Do not warm the syringe. massage oil. to avoid touching the glass part. Insert the syringe through the 1 mm hole of the three-hole adapter. it may draw water out of the needle!). noodles.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. Always use a syringe with a long metal shaft. the sample must release water completely. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. amount 100% Samples Solvents: toluene. Hold the syringe at right angles directly in front of your eyes to read off the value. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric.3. fatty creams Waxes. tar products. lay it down on the adapter and empty it completely. yogurt. creams.

or by indicating the maximum number of samples to be titrated. the water will no longer be completely released. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . and . Sugar is the only type of sample that dissolves in formamide. 2. The solvents that are used should contain as few water as possible (< 100 ppm).3.e. This will lead to incorrect results.salicylic or benzoic acid for basic samples. 4. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. too low water content.g. it is necessary to replace the solvent timely. 38 .imidazole is used for acidic samples. The solvent for the two-component reagent contains SO2. you must replace the solvent timely. which may be completely expended if you titrate a large number of samples with high water content. On the other hand. Once again. formamide effectively extracts water from starch products. 3. In this case. or the titration will take too long and titrant will be wasted.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life. 50°C). starch products will not dissolve in it. the amount of water in mg which has been titrated. i. The amount of formamide at 50 °C should not exceed 30%. The extraction capacity can be improved by increasing the temperature (e. Therefore. If acidic or basic samples are titrated. the titration of subsequent samples will then be very slow. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. If exhausted.

e. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. 2. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. If you have to store the sample. 39 . which cannot be mixed as thoroughly as liquids. the water is not uniformly dispersed. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. The sample should be taken quickly to exclude.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol.e.the most common source of error. the sample should be larger the more heterogeneous the distribution of the water. rinse the bottles two or three times with the sample beforehand. Use sample bottles with small openings to minimize the ingress of moisture. you should take into account the following points: 1. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. This can happen when a sample cools and the water solubility is decreased. the absorption or release of moisture. Use bottles with a septum stopper for liquids of very low water content. The sample must be representative. i. or at least minimize. 3. 5. it must contain the same average amount of water as the material as a whole. you must be extremely careful to exclude atmospheric moisture . "An analysis cannot be better than the actual sample!" When sampling. With liquid samples. and thus air moisture can penetrate the plastic and absorbed by the sample. you should determine its water content as soon as possible. With liquid samples that do not dissolve water such as oils. In such cases. oils.g. water may be separated from the sample if it is left to stand for a long time. 5. such as butter. you will no longer be able to determine its true water content. In the case of non-polar solids. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. 4. the lower the amount of moisture. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry.2 Storing the sample After you have taken the sample. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. Heterogeneous water distribution in samples: In non-polar liquids.1 Taking the sample When taking samples for water determination. It floats on the surface or sinks to the bottom.

This corresponds to 0. the optimum amount of water is approximately 10 mg per sample. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. 10-50 μg water can be detected if the demand for repeatability is not too high.5 to 2 mg water per sample. This corresponds to 7.5 to 17.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5. A titrant consumption of 0.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 . In general. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration.01 10 8 0. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.0 10000 = 1% 0. the accuracy is improved if larger sample amounts are used.1 to 0. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. and the following minimum sample sizes should be used: Water content Min.0 1000 1 1. As a rule of thumb. Repeatable results can be obtained even with 0. it is recommended to use the minimum sample size given in the following table: Water content Min. the accuracy increases with the amount of sample. sample size Amount of water [ppm] [g] [mg] 1 10 0.4 500 2 1. and the required accuracy and precision. the optimum amount of water is in the range from 0. For coulometric analyses.25 100 4 0.1 mg water per sample. If a high level of accuracy is required. Under optimum measurement conditions. because the absorption of air moisture during sampling and sample addition becomes less important.1 to 0.1 1.0 For volumetric titrations.05 mL is thus still acceptable when using a 5 mL burette.05 mg water per sample with a titrant concentration of 1 mg/mL. approx.0 5000 0.3 Amount of sample The amount of sample used depends on • • the expected water content. For optimum accuracy with determinations in the range from 1 ppm to 1% water.08 50 5 0.2 1. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume.

Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Logarithmic scale! 41 . 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content. The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used.

an optimum sample weight range is recommended.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. 42 . which is accessible in the online titrations screen: Dependent on the expected water content.

Inject it into the cell using a wide-bore needle. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. suppositories b c Liquefy the sample in an oven at approx. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. Low water content Low water content Hygroscopic Viscous Very viscous ointments. creams. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. 43 . paraffin. In the case of a volumetric Karl Fischer titrator. This prevents the sample from solidifying in the syringe during the weighing.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. aqueous emulsions. yoghurt. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. benzene glycerol. alcoholic beverages methanol. Possibly warm the sample slightly to lower the viscosity.1 Liquid samples When adding liquid samples. you must take suitable precautions to prevent atmospheric moisture from being absorbed. silicone oil. Fill the 5 or 10 mL syringe with sample after removal of the piston. The syringe is heated together with the wax. 50 °C and fill it into a syringe. especially with samples of low water content. toluene. In the case of a volumetric Karl Fischer titrator. edible oils hexane. hydraulic oils. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. honey a Waxy candle wax. ski wax.

a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Fill a syringe without a plunger with molecular sieves. Fill the syringe with sample and wipe the needle with a paper tissue. Air flows through the molecular sieve into the bottle when you take a sample aliquot. Enter the sample size in the titrator or transfer it automatically. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Replace the syringe with the remaining sample on the balance and back weigh it. use bottles with a septum stopper and pressure equalization. To avoid this. Withdraw the plunger and rinse the syringe with the sample by shaking it. Otherwise when the syringe is removed. – – – – – – – – – – 44 . the drop will adhere to the septum. seal it with cotton wool and insert it into the septum bottle using a short needle. you must aerate the bottle with dry air (equalize the pressure). Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. If the sample is hygroscopic or has a low water content (< 1000 ppm). Start the titration. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". Empty the syringe (into the waste bottle) and repeat the rinsing two or three times.

g. about 50-100 μg water enter the anode compartment. e. depending on the ambient humidity. crystalline samples: Weighing boat – Grind hard. chocolate. solid fat: – Grate the product and add the sample with a spatula. salicylic acid. pulverize less hard samples in a mortar. jellied fruits. cooled analytical mill. For instance. Sample characteristic Brittle Hard/soft Pourable Procedure e. The sample should be quickly weighed and added to minimize air exposure. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. in a volumetric KF titrator solids can be directly transferred into the titration vessel. coarse-grained samples in a closed.when the titration cell is opened to add the sample. salts. the storage of samples in a refrigerator may cause water to condense. If possible. cellulose powder: – Either weigh the sample in a dry box or extract it externally. 45 . – Add the sample with a weighing boat. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. this would lead to an error of 5% to 10%. fatty e. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. thus. Hard.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry .g. e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. it should be added under the same conditions as it was transported and stored. jelly bears. With an optimum sample size of 1 mg water/sample.g.g. For this reason.

This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. margarine. 50 °C and fill them into a syringe. fatty. – Add the sample with a spatula. Back-weigh the empty weighing boat. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. Tare the balance to zero. because the water is released if it is pressurized Waxy e. Do not use a syringe. Use a weighing boat with attached flexible tubing if necessary.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. Add the sample into the titration vessel.g. candles.g. chocolate cream. suppositories: – Liquefy the samples in a drying oven at approx. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. inhomogeneous e. Start the titration.g. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. ski wax. - 46 . paraffin. The syringe is heated up together with the wax. Enter the weight in the titrator or transfer it automatically. The water content is often lower atthe surface than inside the sample. honey. butter. to prevent the sample from adhering to the vessel wall or to the electrode.

e.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. meat. inorganic salts.g. e. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples.g. sausage. The following methods are available: Sample characteristic Very hard Procedure e. fatty Soft. minerals. vegetable juices: Reduce with a homogenizer.g. it is necessary to crush insoluble solids in order to gain access to the trapped water. cooled analytical mill.g. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. water adsorbed on surface capillary bounded water (e. in plants) Water Example: Sugar. e.: • • • • entrapped water water of crystallization (salts).g. fruit juice extracts. This is not the case with solids if the water is bound as.g. brittle Moderately hard. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. noodles. e. Sample preparation Water: Example: Biological samples First of all. organic salts. fatty Mince the product. Fibrous natural products Suspensions 47 . grain.g. berries: Reduce with a homogenizer in an external solvent. e. crystalline products: Pulverize in a mortar. e. jellied fruits. chocolate. e.g.g. coffee beans: Crush in a mixer. hard salts: Grind in a closed.g. solid fat: Grate the product. brittle Viscous Hard. e. cheese: Hard. then reduce it further with a homogenizer in an external solvent. dried fruit and vegetables.

9 0. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.0 7.1 4. sugar. e.5 1.5 8. hazelnuts. etc.8 1. potato chips.9 0. You can speed up the extraction of water from the sample by • • In many cases.4 0.3 1.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. using either methanol or a mixture of it as the solvent.4 1.0 1.g.3 2.8 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.1 mg/pc 3. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.2 1. heating the solution with a thermostating titration beaker.4 1.1 1.8 1. grinding the sample additionally with a built-in homogenizer (see photos below). Water is then extracted providing the mixing time defined in the titration method is sufficiently long.9 srel / % 0.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .

water is extracted from the sample by means of a defined quantity of solvent of known water content. 350 ppm) and toluene (max. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. 49 . pepper. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. butter milk. Briefly.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. The extraction of water can be improved • • • by shaking the solution (mechanical shaker.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. 600 ppm). curry) for dehydrated products for sugar (total water). In particular. Pay attention to the water capacity of chloroform (max. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. edible fat) for natural substances (almonds. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample.

The larger the sample. the smaller the relative error because the total error is calculated with respect to the sample size. A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). the addition of dry quartz sand has proven useful for improving and speeding up the extraction. or use an ultrasonic bath with heating. - 50 . Add a sufficient amount of sample. or use a homogenizer. Shaking is the method generally used for extraction.20 is normally used.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. A dilution factor of 10 . Step 3: Extraction - Shake. For the extraction of tablets.

R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix. 51 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . % or ppm). take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm).

The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.6 61.5 0.3 0.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.4 0.8 54.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.9 11.4 0.5 9.4 0. The weight of the solvent (msol).6 72. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .3 0. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.4 4.6 0.

In particular. Chloroform. Note: 1. 3. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. the formula is automatically given. reaches the saturation limit for water already at 350 ppm! 53 .e. by selecting the appropriate calculation (i.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. The water content of the solvent should be as low as possible. for instance. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. “External extraction”) in the method function “Calculation”. The amount of sample should also take account of the absorption capacity of the solvent. 2.

1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content.2 10. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar.2 1.9 5. or with a very low water content. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results.8 2. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 . ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. or with a high water content Pure solvents can be used to dissolve the samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. in % or ppm.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. the addition of methanol is not necessary. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.

KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. 3. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. In fact. the error as a result of opening the titration stand will be between 10 and 30 µg.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. Rinse the syringe two or three times in this way. weigh it and inject it into the titration cell. the blank value correction is too large compared to the amount of water in the sample. 5. Determine the weight of anolyte injected by back weighing. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. 7. Since you are able to work with larger amounts of sample when working with this technique. 55 . Thus. weigh it and inject it into the septum bottle. 7. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. Direct titration is not suitable. If the solid has a low water content (<200 ppm). Remove approx.g. 6. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. biological tissue. and too much titrant is consumed. 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. On the other hand. this error is reduced. serum. because a large sample amount leads to a too long titration time. Determine the weight by back weighing. the error obtained by direct titration if the titration stand is opened to add the sample is too large.20 mL of anolyte titrated to dryness into the syringe. Draw an aliquot into the same syringe again. Draw 10 . 2.

because the anolyte titrated to dryness has a blank value of "0". Alternative procedure: 1. 5. The water amount in µg is determined. then you can additionally calculate the result can be given in ppm. If you know the lyophilized sample amount in the septum bottle. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. Thus.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. 8. 7. the final result must be multiplied by 4 (factor f = 4). Rinse the syringe two or three times in this way. Since ¼ of the total amount was injected. zero must be entered for the blank value (B). 56 . Remove approx. 3. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. In this way. 2. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. 6. With a standard method calculation and calculate the water amount in µg. 4. the water amount in the septum bottle is 4 times larger. The accuracy of a plastic syringe is enough.

.Purge the sample vessel and the tubings thoroughly beforehand with the gas. time" and a "Delay time" of e. 57 . . The gas must be directed through a water-dissolving. . . hydrochloric acid. depending on the water content of the gas. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel.Stop the gas flow after 1 to 2 mL titrant has been consumed.g.5 Determination of water in gases To determine the water content of gases.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. . .When titrating large quantities of gas in the same solvent. The water content in ppm is calculated by entering the volume and the density. Sampling/sample addition .As soon as the drift is stable again. Determination .Calculate the volume from the time and the gas flow rate.g. the gas must be directed through the titration vessel for a defined period of time. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations.Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. .If possible. .With sample vessels the gas amount gas can be determined by differential weighing. you must fill the gas either into special gas sample tubes or into small steel cylinders. Notes . The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.Select "Max.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. . water-free absorption liquid in which CO2 itself does not dissolve. 600 s as termination parameters.CO2 gas can not be titrated directly since iodine reacts with CO2. to ensure that the titration is terminated after the maximum time.Purge the system with the gas before you start the determination.Turn the three-way valve. to prevent the gas from flowing into the titration vessel. you should titrate the gas sample directly from the source. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. If not. .

7.1 - The recovery rate is clearly decreasing with increasing gas flow rate.7 500 97. For Karl Fischer titration. causing the water in the sample to vaporize. chapter 7. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. for accurate results do not select a too high gas flow rate. which could react with the sample at higher temperatures.: o o air with 50% humidity: approx. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven. e.1 Principle The sample is heated in an oven. and the amount of water is determined. The purge gases commonly used contain moisture.6 Determination using the drying oven This method is suitable for solids and liquids that 1. Air should therefore only be used for non-oxidizable.1 bar (cf. you should use a two-stage pressure regulator so that the final pressure is in the range 0.2 Purge gas Air contains oxygen.6. or 2.6.g. that release water very slowly. The water is transferred to the titration cell in a current of dry inert gas (purge gas).5). chapter 7.4) A gas stream of approx. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.9 166 99. Thus. 11 mg/L nitrogen gas from a cylinder: 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.6. 7.0 mg/L Therefore.4 – 8. 58 . If you use air for organic samples. inorganic samples. the purge gases must be first dried before entering the KF oven.6.5 . If you use nitrogen from a gas cylinder. cf. the oven temperature should not exceed 160 °C. cause side reactions with the Karl Fischer reagent.

80 µg H2O/L 40 . Method 1: The water evolved is continuously titrated After a short mix time (20 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. deactivate the drift stop).60 s). you should set the maximum titration time as the termination parameter (i. all the water is vaporized and transferred to the titration cell. Silica gel and molecular sieves have the advantage that they can be regenerated. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell. they are rapidly exhausted. but their water absorption capacity is low. there are two types of anolyte solutions: 59 . The relative drift stop or the maximum titration time can be used as the termination criterion. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. i.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum.e.e. especially methanol. the titration starts and the released water is continuously titrated.e. In the case of KF coulometers. the vaporization is often very irregular. 2. Silica gel is appreciably better in this respect. With some samples the drift at the end of the titration is significantly higher than the initial drift. in contrast to other desiccants. 7. whereas molecular sieves requires temperatures up to 300 °C. The KF titration is then started. At the end of the titration.6. deactivate the drift stop). In such cases you should use the maximum titration time as termination parameter (i. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. 100% Phosphorous pentoxide.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. Silica gel can be regenerated over night at 150 °C. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. In order to avoid the latter you may also use the minimum time as termination parameter. To ensure that the determination is repeatable. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample.

oven temperature 200 °C: approx. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). time Max. dedicated anolyte to be used with a KF Oven (e. time 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e.5 mL/hour Anolyte containing ethylene glycol. you should replace the anolyte lost through vaporization with new anhydrous methanol. the recovery is not 100%. time Max.7 99.g. 7.e. An air pump is available as an optional accessory.200 mL/min. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . i.6.9 2. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C.g. Coulomat AG Oven): Anolyte loss at 150 . oven temperature 200 °C: approx.95 98. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0.200 mL/min. The procedure for the determination of water content is described in the operating instructions.2 4. The recovery therefore depends on the amount of methanol vaporized and the method used. time Max.g. Due to the vaporization of the methanol. This is particularly important with low-weight samples (e. 3.8 6. as well as a gas flow meter. time Max.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. Examples: Sample Result / ppm No. and the better the recovery.e.1 Briefly: The less methanol is vaporized.9 9.2 99. 1 mL/hour – From time to time. there is a small loss of water. fibers) or with samples of low water content.4. the faster the water is titrated.2 1. It has a large glass sample boat capable of holding up to 10 cm3 of sample. i.5 . time Max. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve.

evaporated solvent does not condense in the drying tube. For instance. and/or replace the anolyte of the KF coulometer. you should proceed as follows: 7.55% or VWR/VWR/MERCK water standard KF oven 1%. 10. To check the performance of the titrator/drying oven system. bent drying tube. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. 3. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. do not select the parameter "Auto start". Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Some samples have surface water that is lost as soon as the oven is purged with dry gas. 5.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. Set a gas flow rate of 150-200 mL/min. start the titration so that the drift value is automatically entered. A large amount of evaporated water cannot be fully absorbed by the solvent. . replace the silica gel and molecular sieves of the gas drying unit. the evaporated solvent lost in the gas stream has to be replaced. If the drift is higher than 15 μg H2O/min. Then. 2. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). 61 9. Close the stop cock and purge the "hot zone". If several determinations are performed in the same solvent. This can happen when the titration is started only after complete evaporation. If the water is titrated as soon as it begins to evaporate. 3.7%. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. purge the "cold zone". Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. the recovery increases to 99. If the drift is constant.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. and does not drop into the cathode compartment/ titration cell. 6. For the same reason. In such cases. in volumetric KF titration the methanol loss is approx. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. Some samples require some time before water starts evaporating. 4. Open the stop cock. This leads to a too low result.

The oven heats the sample to the set temperature. while a glass tube pierces the aluminum foil cover. STROMBOLI is completely controlled by the titrator: all the parameters for the determination.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. 3. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. including the oven temperature. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. The sample vials are moved upward into the oven by a lift. The drying oven can be operated in the temperature range from 50 to 300°C. 62 . are included in the titration method. Besides 14 places for glass sample vials.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.6. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. After the analysis. 1 During a sample series: 2 3 1. The blue rubber cap seals the sample vial tightly against the oven. 2.

This takes 10-20 minutes as can be seen in the following diagram: 63 . Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. The drift value is defined as the moisture entered into the titration cell by the purge gas. the moisture in the empty sample vial has first to be removed.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). This is particularly important with light samples (e. To determine the drift value accurately.g. fibers) or with samples of low water content.

the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. the method contains a so-called sample loop.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. drift value x time). At the start of the method. In the same way. they can be measured at different temperatures using the same method. This means that the stored drift value of the previous determination will be used. for example. 64 . a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. In this case. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. it is important to use a new sample vial for each blank value determination (i. The new blank value is automatically used for the blank correction.e. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396).) are always slightly different. as well as the anolyte in a coulometric analysis.the analysis times for the determination of the blank value and for each sample are the same. If the temperatures of successive loops are different. The blank value should be determined before each series because the humidity can change. suboptimum conditions. Thus. The optimum blank value is in the range of 70 . etc. a blank determination can be performed between two sample loops. In this case. gas flow. The first sample of the next loop is then transferred into the oven and the water determination begins. moisture in the sample vial. For each series.300 μg water. If this is the case. With rapidly changing. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. the moisture in the air present in the vial. one with the same properties as the sample vials into which the samples have been filled in). the blank value determination also takes the actual drift into account. the drift value can change with time.g. you can enter the number of samples the series includes for each loop. To determine the blank value as accurately as possible.e. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. Nevertheless.e. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. different plastic samples have to be analyzed. It is therefore not necessary to perform a drift determination before each series. The loops run through one after the other and the samples are processed sample for sample.e. Performing the drift and blank value determination In general. you can check whether the drift is constant and the new drift value can be used for the next series. The blank value can also vary as a function of temperature. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. whose optimum bake-out temperatures differ. the moisture content is somewhat lower. and thus the moisture adsorbed on the glass walls is not always the same. Important: After a blank value determination. i. These method templates are based on a dedicated KF method type called ‘Stromboli’. > 15 μg H2O/min). the vial used no longer has the same properties as the "fresh" sample vials. If. By performing a drift determination at the end of the series or between several series. If the maximum titration time is used as termination criterion in the method -which is what we recommend. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i.

Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. you can not only determine solids but also liquid samples. and therefore it does not drop into the cathode compartment. bent drying tube. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. 2.g. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. The delivery tube has a T-piece that causes a small leak flow.g.55% or VWR/VWR/MERCK water standard KF oven 1%. evaporated solvent is not condensing in the drying tube. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. see also list of results). 3. This valve shall be used especially if inert gas sources are used. toluene. In this way. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. 6. With STROMBOLI. 4. Use the same vials for a sample series as well as for the blank value determination. 8. since it provides a leak free inert gas stream during normal operation. Set a gas flow of 40–60 mL/min. To check the titrator/drying oven system. This test also serves to check the tightness of the oven and the connection tubing 65 . This has a large effect on the blank value and thus on the result. 7. 5. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. drying and storage). A sudden shutdown of power immediately switches the valve in that way. These are partially vaporized (e. motor oil) or completely vaporized (e.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

Therefore.0 3. A good repeatability is achieved the sample size is increased particularly for low water content values.0 5.0 Sample size (g) In both cases. it is necessary to use the optimum sample size in order to achieve precise results.5 1. with decreasing sample size the relative standard deviation srel becomes worse. 69 .0 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0.25 0.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

71

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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Check whether titration stand is completely tight.Measurement electrode is not plugged in .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .g. drift stop .Use a different method Oven: water not completely vaporized .Replace molecular sieves and silica gel in drying tube .Use higher oven temperature .Homogenize sample.Measurement electrode is faulty Titration stand not protected against moisture . e. drift stop as termination parameter. .Use t(max) as termination parameter .Replace anolyte .Check whether titration stand is completely tight. .Use smaller sample Long titration time.Add a small amount of one-component KF titrant to the catholyte. Water distribution in the sample is not homogeneous . increase t(max) Wrong control parameters .Use rel. if possible increase amount of sample Wrong sample preparation and sample addition .Increase vaporization time.Clean titration cell and generator electrode and dry at 50 – 80 °C .Increase amount of sample to ensure that approx. titration never ends Very long pretitration Poor repeatability Wet anolyte .The repeatability is strongly dependent on suitable sample preparation and sample addition.Grease the tapered joints Moisture from cathode compartment and diaphragm . Oven: .Increase end point Oven: water vaporizes very slowly and irregularly . especially at low water content (< 1000 ppm) 73 .Replace anolyte Amount of sample too small .Higher oven temperature .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Increase value for rel. 1 mg water per sample is present. .Clean the platinum pins of the measurement electrode with paper tissue .Level of anolyte should be higher than that of the catholyte .Lengthen vaporization time (increase t max) .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .

Replace anolyte .Extend tmin (minimum titration time) Incomplete sample addition .0 or 0.Check drift and blank value .Too low value: see above “too low value” if this does not help.Use fix generator current 100 mA .Use back weighing. .Too high value: see above “too high value” . If the sample preparation and addition is not done carefully. Checking drying oven Out of limits. check generator electrode.1 mg/g . bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .Sample not thermal stable: Use lower oven temperature .Add sample into KF reagents.2 .Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . Anolyte has too low conductifity .Reduce the value for rel.0. at 170 °C.Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. if it is defective.use a bigger sample size up to 0.Replace or change the anolyte . 10 – 15 minutes . It has no influence to the result. Sample not dissolved (emulsion) .Replace anolyte If this doesn’t help.Use start cautious Oven: . bad repeatability With water standard 1. contamination with atmospheric moisture occurs.Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.Use smaller sample size Values too high The titration was too fast → overtitration . For samples with very low water content < 30 ppm .Lengthen vaporization time (increase t max) .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . the Coulometer must be adjusted With water Standard KF Oven 1 %.3 g Generator electrode is contaminated The black cover cannot be removed. drift stop . .Replace or repaire generator electrode.Use higher oven temperature . do not splash to the walls of the cell.

Increase endpoint potential Oven: water vaporizes very slowly and irregularly .Extend vaporization time (increase t max) . external extraction. drift stop" as a termination parameter.Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture . Low water content (<1000 ppm)! . Oven: water is not completely vaporized . etc. e.Use different method. 75 .Check whether titration stand is completely tight. Wrong control parameters .Increase value for relative drift stop. e.Check and optimize control parameters.g. . Titration stand not protected against moisture .Increase amount of sample to ensure 10 mg water per sample.2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration .Use t(max) as termination parameter .Homogenize sample. if possible increase amount of sample.Grease the tapered joints Condition Titration stand .Use higher oven temperature .Use "Rel. Side reaction of the sample with the KF reagent .Replace molecular sieves and silica gel in drying tube .Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker.Extend tmax (maximum titration time) .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water . . Water distribution in the sample not homogeneous .Reduce sample size Poor repeatability of the results Amount of sample too small .The repeatability is strongly dependent on suitable sample preparation and sample addition. .Clean platinum pins of the electrode with a paper towel. titration never ends Wrong termination parameters .Increase oven temperature .Increase vaporization time. increase t(max) Long titration time.see above Oven: . drying oven.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10.g.

Use back weighing. If the sample preparation and addition is done carefully. contamination with atmospheric moisture occurs. Sample not dissolved . Poor sample preparation and addition .Extend vaporization time (increase t max) .0 is a simpler and a more dependable method. No more sulfur dioxide in the solvent .Reduce dVmax and dVmax factor.4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) . which dissolves the sample.Reduce the value for rel. For samples with low water content < 400 ppm . 15 – 20 minutes . bad repeatability 76 . Determination of the concentration using di-sodium tartrate or Water Standard 10.Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Change solvent or use fresh solvent after every sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . Oven: .Change solvent.Replace the solvent frequently.Extend tmin (minimum titration time) Incomplete sample addition .Add chloroform or other solvent to methanol.Use higher oven temperature . .12 g in 40 mL.55 % at 220 °C. Di-sodium tartrate has only limited solubility In methanol max. The concentration determination is correct only if the di-sodium tartrate has completely dissolved.Use titrant with 2 or 1 mg/mL Oven: .Samples of low water content (<1000 ppm) are always hygroscopic.Check drift and blank value . 0. drift stop .Replace solvent . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results. With water Standard KF Oven 5.Sample is not thermally stable: Use lower oven temperature .Increase sample size up to 0.

V3. anisidine. e.g.V5 C20.pyren e.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. diphenylmethanol Weakly basic pKa >8: Imidazole.V5 C20 Ethers Linear and cyclic V2.1 Solid samples 11.V3 C20 di-Nitrobenzene. V4 C20 V2. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl. o-cresol Side reaction: naphthol. V4 V2. C0 Peroxides V2. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0.V4. salicylic acid High pKa value: 2-chlorophenol. cresol.V4. naphthalene > C20 Tar. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 . anthracene. C0 Sulfur compounds Phenols V0.C22 V16 C0 V10 C0 Nitrocompounds V3.V3. C0 V2. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0. nitrotoluene.V8 C20 V10. bitumen V4.V5 C20. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. V3. C0 V2 C20 V15 Low pKa value: phenol.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. R-I R-NCO Benzophenone Method V2.V3. V4 C20 Mercaptans V0. C20 V11 C0 V2. V3. V5 C20 V2.C22 V2. oxalic acid Oxidizable with iodine: ascorbic acid V2. V4 C20 V15 C20 V0. C24 Hydrocarbons > C12 Biphenyl.: benzamide. R-Br.V4.V4. nitrobenzaldehyde > C12 Stearyl alcohol.1.V7 V2. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. V3. indole. toluidine Oxidizable with iodine: aminophenol Method V2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11.

glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. CaO NaCl. V8 Cosmetics Creams. ZnSO4 V2. 78 . dispersion dyes Waxes. V30 Insecticides.g. paraffins: shoepolish. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. CaCl2 . H3BO3 NaOH. V31 C31. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. V32 C20. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . Insoluble: pigments. e. NH4NO3 Nitrites NaNO2 11. V31 C32 V2. polystyrene.1.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. multipurpose grease V2 V2. V5 V5 V2 V20 V2 V5 V30.C40 V2 Adhesives All-purpose glue. etc. C34 V10 Na2HAsO3 . herbicides Soluble: wool dyes. bitumen lubricating grease. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2.: Na3PO4 Silicon oxide. C34 V31 C33 V2. fungicides. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . indicator dyes. poly-amides. Phosphate.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. V32 C21. KJ. lotion Lipstick Soaps Toothpaste V4. Na2HPO4 tert. C34 V2. polyurethane. V5 V12 V2 V40. HBO3 . polypropylene. disinfectants Salves.1. PVC. Silicon dioxide Silanols R3Si(OH) Na2SO4. etc. C32 Pharmaceuticals Antibiotics. KOH MgO. C34 V2. V31 C20. creams Suppositories Tablets Lyophilized preparations V2 V4. NaAsO2 KHCO3 . V31 C20. NaHCO3 Na2CO3 B2O3 . V32 C21. ski wax Tar. V31 C20. C32 V15.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. V32 C20.

1. tobacco. mixed spice Mustard Adherent moisture: plain salt. gummi bears.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. (V30) Cheese.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. noodles. meat spread.1. Zwieback. V23 Vegetable products V22.almonds instant coffee Fats Butter. jam Honey. plaster. curry. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. V21 Mortar.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. perborates) without brightener Total water V30 V2 11. mayonnaise Shortening.. margerine. caramel. broth Biscuits.4 Technical products . C30 V2 V20 Paper. jellied fruits. sea salt Total water: plain salt. ice cream Dried albumen Powdered milk V2 V13 V2. wheat. hardened fat V4. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. candy. rye.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. jelly Sugar: adherent moisture Chocolate Spices Pepper. sea salt V23 V24. pudding powder. coffee beans. noodles. tea. (V25) V22. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . almond paste Instant ice tea.1. V23 V30. dried vegetables and fruits Hazelnuts. instant coffee. wood Cellulose powder Wool. potato chips Potato flakes Dough. Zwieback Yogurt. silk 11. V23 Cacao. corn.

nitrotoluene. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. ethylal. ethyl acetate Methyl chloride. isobutane. HNO3. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. anisole Methyl benzoate. toluene. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. paraffin Aldehyde Acetaldehyde. toluidine. crude oil. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. acetophenone.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. C1 Sulfurcompounds V1 C1 V0. HCl Nitrobenzene. cyclohexene. chlorotoluene Acetone. chinoline Strongly basic: alihatic amines N-butylamine. dioxane. diamine Easily oxidized with iodine: hydrazine. t-butyl chloride. benzene. chlorobenzene.2. acetic acid > C2 propionic acid. cyclohexane. methylal C1 to C7 hexane. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides.2 Liquid samples 11. methylethylketone Ketones V10 C10 80 . disulfides sulfonic acids Mercaptans V1. hexanol. pentane. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. dodecane > C14 heavy oil. xylene C7 to C14 gasoline. petroleum. hexylamine Reaction with methanol: aniline.

transformer oil. refer to chapter 11. brake fluid. liquor Pharmaceuticals: extrakts. 81 . sample input and titration methods. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer.3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. sunflower oil Pharmaceuticals and cosmetics: ethereal oils.2. wine. tinctures Cosmetics: perfume. cream. massage oil Vegetable oils Technical oils Hydraulic oil. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk.

reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .3 Titration Methods 11.3.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . These can be also performed using the one-component reagent.10 minutes Direct titration methanol free Titrant: two comp.10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .120 s Delay time: 7 seconds. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 . In this case methanol is used as a solvent.1 Volumetric methods The methods have been developed using 2-component reagents.

50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat. Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .20 min With drying oven at 160 .

3. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.

8 mm ) Fill in backend of syringe Procedure Grind in sealed. wool. Use grate to reduce size. rocks e.g. Use syringe with needle Ø 1. S2 S1. coffee. tea. napthalene. active ingredients Na-tartrate S9 S12 11. S5 S10 S8 Paraffins.1 Solids: Characteristics Property Very hard Hard. Stir. paper. S3 S10. greasy Soft.4.4 Sample preparation and input 11. formamide). or up to approx. meat grinder. pepper.) S8 S9 S10 syringe with needle Ø 0. Homogenize sample well. resinous Waxes Examples Butter.4. 1-decanol. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. SiO2 Salts. After sample removal keep sample sealed. Inject into titration cell. Cut in small pieces with scissors or knife. silk Cheese. 60° C.) Homogenize sample well. gummi bears. brittle Soft. In external extraction solvent (methanol. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. shake or sonicate. ice cream. noodles. S11 S4. creams gel.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. meat Jellied fruits. tobacco. bitumen Method S7. Pulverize with mortar. Pulverize with mixer. Press through small holes e.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. cristalline products Wheat.5 mm or without needle. At room temp.: CaCO3 . Melt sample. honey. shoepolish Creams. No further preparation necessary. Let solids settle and remove aliquot of remaining solution with syringe. chocolate Method S1 S1. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 . yogurt Salts. potato flakes Tar. almond paste. jelly. formamide). Zwieback Dried vegetables and fruits. S11 S6. S10 S11 S4. S8 S10 Property Soft. S10 S11 S10. broth Hardened fat. almonds.g. 1-decanol. greasy Examples Minerals. Dissolve sample or extract water. cooled analysis mill. After sample removal keep sample sealed. margarine Phenols. (Pre-heat syringe with hair dryer or in drying oven. pastes Pulverized soluble Salves. S10 S2. S3 S2. for very thick pastes drill hole in bottom of syringe. (Select stir time so that sample dissolves completely.

toluene.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. . cream Method L1 L2 L3 L4 L4 L1 L5 L6 11.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0. . salad oil Perfume. Hygroscopic sample or low moisture content (< 1000 ppm) .4.4.Homogenize thoroughly by shaking or stirring prior to sample removal. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 .Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. crude oil.Remove sample immediately. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. acetone. glycerine Acetaldehyde Methanol. acetone.8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 .4. 11.5 mm) Injection with syringe after cooling sample (with needle Ø 0. H2SO4. glycerine Hexane.15°C Examples Propanol. glass Visco-Spoon™ 1 mL ME-71492 1. aqueous emulsions Acrylic enamels. Boiling point 5 .15 °C . after-shave Beverages. .8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm) Injection with syringe (without or with needle Ø 1. .8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. synthetic enamels. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. For each titration use 1 mL syringe (with needle Ø 0. milk.5 Accessories for sample input Syringe Injection needle Weighing boat.The pressure loss during sample removal must be compensated with dried air. detergents. gasoline. . 0°C in ice bath.Cool sample to approx.8 mm). .3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic.8 mm) Inhomogeneous emulsions . acetic acid Silicon oil.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.Keep sample in a septum flask. petroleum.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.

705-717 (1976).. Chem 368. Part III. Anal. 71. G.. W.. K. Part V. MITCHELL jr.2412 (1939). 15 (4). “Reaktionsmechanismen in der Karl-Fischer-Lösung“. SEUBERT A. Chem. [8] SCHOLZ. BARENDRECHT. Anal. SCHOLZ. „Kinetics and stoichiometry in the Karl Fischer solution“. E. Anal. See literature references in: EBERIUS. Anal. Electroanal. 86. Electroanal. 303. Diploma-Thesis at the University of Hannover / Germany. PhD. 2407 . Electroanal. 334. [3] [4] [5] [6] [7] 87 . „Wasserbestimmung mit Karl-Fischer-Lösung“. VERHOFF. BRYANT. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. SMITH..M. 334. Rotating ring disk electrode meassurement“. Einkomponenten Reagentien“.S. WERNIMONT. J.C. W. “Analytical Procedures Employing Karl Fischer Reagent I. J. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. SCHOLZ. 93. J. 395-403 (1977). HOPFKINSON.. Anal. VERHOFF. 61. Nature of the Reagent”. Eng. BUNSEN.W.396 (1935). 48. 272 – 274 (1943). 312. Anal. “Mechanism and reaction rate of the Karl Fischer titration reaction. 309.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. J. 30-32 (1981). P. C. „Karl-Fischer Reagentien ohne Pyridin. 407-415 (1978). Chem.. [9] WÜNSCH. S. 94. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. Chem. G. Fresenius Z. Soc. 16-21 (1989) (in German). WÜNSCH. J. BOYD. Chem. Thesis University of Hannover. Fresenius Z. 75. Fresenius Z.. SCHOLZ. M. „Karl-Fischer Reagentien ohne Pyridin. E. G. 394 . Part I. Both publications from: SEUBERT. G. Analytical implications”. W.C. 75-80 (1978). “Mechanism and reaction rate of the Karl Fischer titration reaction.. Part II. Anal. Chem. 86. F. 123-125 (1981). Chem.. “Karl-Fischer Reagentien ohne Pyridin“. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. E. Electroanal. M.6 References [1] [2] FISCHER. Chem.. Liebigs Ann. “Mechanism and reaction rate of the Karl Fischer titration reaction. Chem. R. Z. J.. 203 .comparison with the aqueous system“. VERHOFF. Chem. SEUBERT A. Auflage. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”.. E. 305-315 (1976). A... S.. GRÜNKE. 394 . 460-464 (1982). E. Anal. J. 139-147 (2000). Anal. BARENDRECHT..C. Fres. Neue Eichsubstanzen“..C. 215 – 219 (1959).. VERHOFF.. Zweikomponenten Reagentien mit Imidazol“. BARENDRECHT.207 (1980). J. 265 (1853). “Mechanism and reaction rate of the Karl Fischer titration reaction. Acta. Chem. Part IV.. Ed. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“.. Th. SCHOLZ. [10] GRÜNKE. Rotating ring disk electrode meassurement . Anal.. D. 1988 (in German). „Karl-Fischer Reagentien ohne Pyridin. 306. First and second order catalytic currents at a rotating disk electrode“.C. 256-260 (1989) (in German). Amer. 1.396 (1981). MEYER. Chim. Chem. E. Angew. Potentiometric measurements”.. Z. Chem. Fres. Fresenius Z. 1999 (in German). .J. “Untersuchungen zur Karl-Fischer-Reaktion”. J.. Fresenius J. A. VERHOFF. Chem. Ind. J. WÜNSCH. E. E. 31 (2). Chem. COFINO.. 309. J. Chem. KOK. Anal. Verlag Chemie Weinheim (1954) / (in German). Fresenius Z.. E. „Mechanism and reaction rate of the Karl Fischer titration reaction. Chem.4..

„Eugen Scholz Reagents for Karl FischerTitration“. DE CARO C. Sigma-Aldrich Laborchemikalien GmbH. „Karl Fischer Titration“. D. M. 11. Diploma-Thesis at the University of Hannover / Germany. Springer Verlag Berlin.5 Additional literature HYDRANAL®-Manual... 1989 (German) 88 .. 1985. Darmstadt / Germany.. K. 431-435 (2006). GIT Verlag GmbH. Food Chemistry 96. SCHOLZ.30918 Seelze / Germany. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications".. E. „Wasserbestimmung durch Karl-Fischer-Titration . WIELAND.A. SCHÖFFSKI. „Untersuchungen einer Karl-Fischer-Reaktion“. 1984.. DE AGOSTINI A.METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ.Theorie und Praxis“.. G. RÜEGG K. 2006.

WP: This is what we get from the calculation in the KF method. The sample P used for the extraction is not dissolved. 89 . % or ppm). Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm).1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm.

ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. Total water content (sample + solvent). in % or ppm.01% VWR/VWR/MERCK APURA water standard 0.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. 90 . Blank value (water content in% or ppm) of the solvent. The sample P used for the external dissolution is completely dissolved into the solvent. the total volume is increased.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. Thus. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample.

nitrocompounds. etc. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. i. hydrocarbons (C10 to C20). chlorinated hydrocarbons (up to C10). In this case. ointments.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. This means that if an emulsion is formed in the anolyte. more solvent can be added to the anolyte. This is limited to a maximum of 30% to prevent the conductivity from falling too low.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10).4. Alternatively. part of the water content is not measured.4 Reagents and solvents for coulometric analysis To determine its total water content. an emulsion is formed. the anolyte must be immediately replaced. ethers.4. If the sample does not completely dissolve.e. the sample must completely dissolve in the anolyte. the water content determined is lower than the actual water content of the sample. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12. etc. edible oils. 12. esters. A number of different anolytes are available to dissolve the various types of samples encountered in practice. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. alcohols. acetamide.

4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. hydrocarbons (above C20). For cells without diaphragm: - Notes on ketones: - - 92 . transformer oils. If you measure ketones regularly. Chloroform must be added to the anolyte to ensure the solubility of these samples. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low.4. etc. silicone oils. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. we recommend the use of a second titration cell. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12.4.

5 to 7 (see Section 1. The special reagent for ketones can also be used for other samples. however. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. amines: - 93 . After a longer standby period. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed.e.g. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). the drift is higher because of the very slow side reaction. i. etc. Fill the anode compartment with approx.g. acetaldehyde) are oxidized at the anode with the formation of water. The measurement should not be performed in the titration cell because the electrode introduces too much water. - For acidic samples. Short chain aldehydes (e. the pH value of the anolyte must be adjusted to the range 5. In these cases the pH value of the anolyte should be measured. Aromatic aldehydes (e.METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. 1 mL). It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. It is important to note that alcohols that react with ketones should not be titrated in this reagent. e. Choose relatively small samples (approx. Measure the pH with a glass electrode adjusted with aqueous buffers. formic acid. take an aliquot of anolyte from the titration cell. Fill the anode compartment with approx. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. benzaldehyde) can also be determined by coulometric KF titration.2 mL to 0.g.2). Coulometric KF titration cannot be used to determine these compounds.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift.g.4.5 mL. the substances can. The larger the sample. To do this. With Karl Fischer titrations of acidic and basic samples. Basic samples must be neutralized with salicylic acid or benzoic acid. acetic acid. Use the HYDRANAL® buffer (SIGMA-ALDRICH). with reactive ketones such as cyclohexanone use only 0. - - Notes on aldehydes: - - 12.: - For basic samples. easily be measured with volumetric KF determination. The use of imidazole increases the pH value in the anolyte. e. the more important the effect of side reactions becomes. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. 80 mL of anolyte and 20 mL HYDRANAL® buffer.

ethers. an emulsion is formed. the result determined is lower than the actual water content. In this case. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. alcohols. This is limited to a maximum of 50%. etc.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. If it does not completely dissolve. The water content is declared on a test certificate supplied with every vial.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5.6.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0.6. In this case. A number of different anolytes are available to dissolve the various types of samples encountered in practice. nitrocompounds. ointments. etc. part of the water content is not measured. edible oils. i. 12. more solvent can be added to the anolyte 12.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. hydrocarbons (C10 to C20). Alternatively. acetamide. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. One-component reagents: 94 . the anolyte must be immediately replaced.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1.2 For samples poorly soluble in methanol or ethanol These include: etherial oils. chlorinated hydrocarbons (to C10).55% (potassium citrate monohydrate).e. esters.

6. or an acetal. transformer oils. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. with the formation of water. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. etc.3 For samples insoluble in methanol or ethanol These include: petroleum oils. One-component reagents: 95 . Chloroform must be added to the anolyte to ensure the solubility of these samples.6.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low. hydrocarbons (above C20). silicone oils. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances.

g. take an aliquot of anolyte from the titration cell. amines: 96 . e. The larger the sample. e.g. acetaldehyde) are oxidized at the anode with the formation of water.: - For basic samples. easily be measured with volumetric KF determination. Coulometric KF titration cannot be used to determine these compounds. however.e. 80 mL of anolyte and 20 mL HYDRANAL® buffer. If you measure ketones regularly. To do this. the drift is higher because of the very slow side reaction. The measurement should not be performed in the titration cell because the electrode introduces too much water. The use of imidazole leads to a high pH value in the anolyte. 1 mL). Fill the anode compartment with approx. Measure the pH with a glass electrode adjusted with aqueous buffers. Choose relatively small samples (approx. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte.g. the substances can.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. If you have titrated a number of ketone samples. Use the HYDRANAL® buffer (SIGMA-ALDRICH).5 mL. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value).5 to 7 (see Section 1. etc. It is important to note that alcohols that react with ketones should not be titrated in this reagent. with reactive ketones such as cyclohexanone use only 0. In these cases the pH value of the anolyte should be measured.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference.2 mL to 0. The special reagent for ketones can also be used for other samples. Short chain aldehydes (e. formic acid. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. - For acidic samples.6. - Notes on aldehydes: - - 12. acetic acid. the pH value of the anolyte must be adjusted to the range 5. the more important the effect of side reactions becomes. i. Aromatic aldehydes (e.g. benzaldehyde) can also be determined by coulometric KF titration. With Karl Fischer titrations of acidic and basic samples. we recommend the use of a second titration cell.2).

Fill the anode compartment with approx. Disposal: as an organic solvent. Keep away from open flames or sparks. Safety: Highly flammable. Keep container tightly closed and far removed from open flames or sparks. buffer (imidazole). 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Irritant when inhaled. 13. Safety: flammable to extremely flammable.: 46 °C MAK value: 5 ppm Flammable. xylene or trichloroethaylene). 13. Health hazard when inhaled.: 28 °C MAK value: 100 ppm Flammable. Poisonous when inhaled or swallowed.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . Irritant when inhaled.1 One-component reagent Composition: sulfur dioxide. Ignition temp. The KF solvent contains: sulfur dioxide. Keep away from open flames or sparks. Disposal: as an organic solvent. swallowed or allowed to contact skin.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. swallowed or allowed to contact skin. buffer (imidazole) and solvent (methanol. Ignition temp. Do not let reagent contact skin or eyes.: 87 °C Ignition temp. buffer (imidazole) and solvent (methanol. 2methoxyethanol or diethyleneglycolmonomethylether). oxidant Ignition temp.1 ppm. 2-methoxyethanol). swallowed or allowed to contact skin.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. Health hazard upon inhalation. Disposal: as an organic solvent. Keep container tightly closed. 2methoxyethanol or diethyleneglycolmonomethylether). chloroform. and solvent (methanol.: 11 °C MAK value: 200 ppm Highly flammable. sulfur dioxide. iodine. Do not let reagent contact skin or eyes. 13. Irritant when inhaled. Health hazard when inhaled. Ignition temp.2 Two-component reagent: Composition: iodine and solvent (methanol.3 Reagents for coulometry: Composition: iodine. Keep container tightly closed. poisonous when inhaled or swallowed. Health hazard when inhaled. Skin irritant. 2-methoxyethanol. Safety: flammable to extremely flammable. Do not let reagent contact skin or eyes. Potential teratogen. 13 Hazards and waste disposal tips 13. tetrachloromethane.

Ignition temp. Ignition temp. Irreversible damage possible.: 6°C MAK value: 20 ppm Extremely flammable. Potential teratogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.: 95 °C Irritant for skin and eyes. Health hazard upon inhalation 98 .: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp.

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development of SOPs and maintenance of the validated state of the analytical system. ©09/2009 Mettler-Toledo AG Printed in Switzerland. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. www. method validation. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. Routine operation including PQ.mt. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators.e. evaluation. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. Evaluation of the appropriate titration system (DQ) i.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. Switzerland Tel. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. ME-51725145A Markt Support AnaChem . specification of the analytical requirements and purchase decision 2.com For more information Mettler-Toledo AG.

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